Bituminous saturant



Nov. 10, 1953 J. c. ROEDIGER BITUMINOUS SATURANT Filed March 29, 1951 NQAI in. m@

nvenoof 6 Iv Mi E Joseph @.Qacdig er Patented Nov. l0, 1953 2,658,857"BITUMINoUs sA'rUaAN'r Joseph C. Ruediger, Statenlsland, N.

to Standard Oil Develo l -porationuof Delaware Y., assignor pmentCompany, a cor- Application March 29, 1951, serial No. 218,136

L4y claims. (C1. 19e-49) f l This invention relates to an improvedbituminous product for use in saturation of iibrous materials employedas structural forms for underground conduits, weatherboard, siding,insulat- Aing board. The saturant serves to improve'the stiffness anddurabilityiof the fibrous material, and principally imparts resistanceto Water absorption-and permeation which is necessary since the fiberboard `disintegrates incontact with "Waten In recent years, suitablebituminous saturants meeting 'the requirements have -been coal tarpitches and the tars available from the Ithermal v'cracking of gas oils.e The coal tar pitchesahave never Vbeen `available in adequate volume,and possess a strong odor which has severely` limited their use vforsaturation of building materials such as weatherboard, siding andinsulating board. With the adventof catalytic cracking processes,thermal ,cracking of gas' oils has 'been essentiallyV discontinued sincethe gas oils are the major feed stock for the catalytic process. kThishas' resulted in a shortage ofk suitable saturant. InvestigationsV haveshown Vthat`v the `normal "straight reduced or oxidized asphalts whichcan be prepared from vbottoms obtained by ,distilla- `tion from, crudeoil, or the tars '.producedfby light thermal cracking (visbreakin'g) ofthe crude bottoms are not generally satisfactorysaturants Vsince theyeither require relatively high temperatures or longer saturating times,or both, to effect ,satisfactory and ample saturation of the fibrouscompositions. l

It is accordingly the principal object` of this invention to provide aprocess for preparing an asphaltic saturant yvvhichfwill yield lanadequate supply of a saturant yeasily 'meeting trade specifiI mations.'e, j' l 'It is a further object 4of the invention'to provide -a processvfor the.; preparationrof l ,such a saturant which` process overcoiries`Yvantages rpointedout above. ,y a Y y r,

` kThe foregoing and other objectsY arer achieved, in'ac'cordance withthe invention, by the thermal cracking of the cycle oil or clarifieroilv obtained in a conventional uid catalyst cracking operation and thendistilling the tarfraction obtained to the desired consistency. By cycleoil or clarified oil is meant the heaviest material taken overhead froma iluid -crackingreacton Entrained catalyst accumulatesin thelieavyfraction and is separated therefrom by settling. The clarified oil thusobtained is then thermally cracked in accordance withthis invention.y cu The type of bituminous materialthat can `ibe employed as saturants isrestricted to thosematerials which have suitable hardness at normalambient temperatures in order to providea saturated product With theproperv rigidity, and

whichv possess k.high susceptiblityto `tempera-.

ture so that the saturation can be accomplished rapidly and at lowestpossible temperature. The permissible saturation temperature is.particularly important since the major bers lused for thesefabrications are organic in nature and can'- not withstand pronouncedexposure to high temperatures without charring, embrittlement or loslingstrength due tothermal degradation. Therefore, any successful saturatingor impregnating `proces-s must be conducted at a temperature reasonablylbelow the temperature of incipient "disintegration "and must beaccomplished in "as short a period as possible, not only to provide amore economical process, but to minimizel the time at high temperature.It should be appreciated that time as Well as temperature yaffecty thedegree of thermal disintegration.' For example, with sugarcane fiber(bagasse) the incipient d]- gradation temperature is about 475i E., butsome degradation 'will occur if the fiber is heldfor onehalf minute orlonger at 450 F. Relative hardness is indicated by the A. VS. T. Mpenetration value ofthe bitumen at '77 F. Likewise, in'order to insuresaturation at temperatures that are not excessive, the viscosity at someelevated'temperature-say, 2'75"V F. or 300 F.-Vis normally specified.`These two properties, penetration at '77 F. and Furol viscosity at 275F., 'can be related by means of a fluidity index which is :A eFluidi'tyindex= f K O (vis. at 275 E; -g'p'enet 77 r.')' pel1g7 Satrantshavingr a low index value are better uited for thepurpose than those ofhigher in- CIEX-` 5 ',Typical examples ofV various bitumens, their-iiuidity index and saturatingvqualities are as follows:"."

softening point F 140 143 144 128 141 138 Penetration 77 F 7 6 7` "57 2818 Furol visc.: 250 F 132 171 240 2759.*11 54 67 130 365 500 290 y 300 F36 43 70 2l() 265 149 Temp. 9 E. for 50 furol 283 293 314 364 390 350Fluldlty mdex 3. 3 3.7 8. 6 176 132 49 Saturatin'gability: 2 l 350 F. GG G P P .P 400 1F G G G P F g F- 425 F G G G P 'Gc G I Min. temp. forgood Sat.- F 350 350 S50-400 425 425 -1 Straighty reduced or partiallyoxidized asphaltsfrom Colombian or Californian crudes`- 2`Ability toyield a fiber board (bagasse type) with uniform surface saturatlon freefrom ffat spots, .f I

It will ybe noted that the tars of columns 1 and 2 permit satisfactorysaturation of bagasse type fiber board, i. e., a smooth, uniform and drysurface free of fat spots results when the board is dipped into a bathat the temperature indicated, for a period not exceeding 30 seconds.

The asphalts of columns i and 5, which represent the normal asphalts ofthe trade, saturate satisfactorily but at a higher temperature (425 FJ.However, it will be noted tha-t the hardness at ambient temperature, asindicated by the penetration at '17 F. is 18 or higher, which is notconsidered sufficient hardness to meet the requirements. Generally, `apenetration 77 F. not exceeding ll is needed. Thus, the only suitableproducts are those of columns l and 2. As previously stated, the tarfrom thermal cracking of gas oil is no `longer available in reasonablequantity to meet the demand. However, the tar from 4the -thermal.cracking of the .cycle oil from catalytic cracking has better over-allqualities than that from gas oil cracking, because the catalytic productis more aromatic in character. The fluidity index demonstrates this, the`catalytic tar product showing an index not exceeding 4, whereas theIgas oil tar generally has an index in the range of 8-12. Inspection ofthe indices of the asphalts from other crude sources also show thatthese products vare high in index and less de- Sirable.

.For a further understanding of the invention reference may .be had tothe accompanying drawing in which the single figure is an elevationalView generally diagrammatic, showing a now plan embodying theimprovement of the present invention.

Referring specifically to the drawing, a hydrocarbon petroleum fractionboiling in the gas oil boiling range (3801000 F.) is introduced intofluidized solids reactor i by means of feed line 2. Reactor is filledwith catalyst maintained by conventional means in a pseudo-liquid stateby the incoming feed vapors. The feed is introduced into the catalystline 3 connecting regenerator 4 with reactor Temperature and pressureconditions in reactor are adjusted so as to secure the desiredconversion of the feed oil. Spent catalyst is Ywithdrawn from reactor bymeans of line 5 and passed into a fiuidized solids regenerator` unit 4wherein temperature and pressure .conditions are adjusted to secure thedesired revivication of the catalyst. Air or oxygen-containing gas isintroduced into regenerator 4 by means of lines 6 and Combustion gasesare withdrawn overhead from regenerator 4 by means of line 8. Thesecombustion gases as they flow upwardly in zone 4 contain finelyentrained particles of catalyst which particles are removed by means ofcyclone separator units 9 and |0 disposed in the upper area of zone 4.The uidized solids cracked products are removed overhead from zone bymeans of line I9 and introduced into a distillation zone 20.

Temperature and pressure conditions are adjusted in zone to remove aheavy fraction by means of line 2|; a heavy gas oil fraction by means ofline 22 and a light gas oil fraction by means of line 23. A fractionboiling in the motor fuel boiling range is removed by means of line 24.Gases are passed upwardly through an absorption section 25 andcountercurrently contact a downflowing absorption oil which ispreferably separated from the light gas oil by means of line 26 andintroduced into the top of the absorption section 25. Gas substantiallycompletely free of normally liquid hydrocarbons are removed overheadfrom zone 25 by means of line 21 and handled as desired.

The heavy fraction is withdrawn through line 2| and passed to clarifier28 Where entrained catalyst is settled out and removed through line 29.The xclarified oil is withdrawn through line 30 and introduced intocracking coil 3| housed in furnace 32. Cracked products are withdrawnfrom furnace 32 through ling 33 and introduced into `distillation column34 Where temperature and pressure conditions are adjusted to remove amotor fuel fraction as a side stream through line 35 and a heavy tarfraction of the desired viscosity by vline 35. Light gases are removedoverhead through line 37|. This heavy tar fraction is the saturant ofthe present invention. If de- .sired the conditions in tower 3| may beso adjusted that the distillation is carried out under vacuum thusincreasing the overhead yield and increasing the viscosity of the tarbottoms.

The fluidized solids techn-ique for processing feed fractions, as forexample, petroleum hydrocarbons and for carrying out other chemicalreactions is a conventional one.

The .conditions obtaining in the thermal cracking zone 32 are alsoconventional and are .in the range between 850 F. and 1200 F. preferablybetween 900 F. and 1000 F. Pressures may vary from 300 to 400 lbs. persquare inch to as much as 1000 lbs. per square inch.

Example A heavy tar fraction obtained from a fluid catalytic yoperationand having a gravity of 19.2 API, '72.5% of which boiled above '700 F.was thermally cracked at 600 p. s. i. g. and 950 F. coil outlettemperature to produce 36 volume percent of gasoline having an end pointof 430 F. .and 62% of tar bott-oms having a gravity of about 2 API. Onvacuum reduction this tar gave a 26% yield of a saturant having F.softening point and with excellent properties.

The nature of the present invention having been thus fully set forth andspecific examples of the same given, what is claimed as new and usefuland desired to be secured by Letters Patent is:

l. Process for preparing bituminous material, suitable as a saturant forfiber board and other purposes, which comprises subjecting the cycle oilfrom a catalytic cracking operation to thermal cracking said cycle oilhaving a gravity of 19.2 API, 'ml/2% of which boils above 700 F. andthen distilling the tar fraction to the desired consistency.

2. Process for the preparation of bituminous material, suitable as asaturant for liber board and other purposes, which comprises contactinga hydrocarbon feed stream in a reaction zone in the presence of uidizedcatalytic particles under temperature and pressure conditions adapted tocrack said hydrocarbons, fractionating said cracked products to obtain aplurality of fractions including a high boiling fraction having agravity of 19.2 API, 721/% of which boils above 700 F. subjecting thehigh-boiling fraction in the absence of catalysts to temperature andpressure conditions adapted to crack the same, distilling the resultingthermally cracked products to obtain a bituminous product having thedesired viscosity.

3. Process as defined in claim 2 wherein the pressure in the catalyticcracking zone is in the range from about 0-30 lbs. per vsquare inch gageand wherein the temperature in said catalytic reaction zone is in therange from about 800 to 1000 F. and wherein the pressure in said thermalcracking zone is in the range from 300 to 1000 ibs. and wherein thetemperature in said thermal cracking zone is in the range from about 850F. to 1200 F.

4. Process as defined in claim 3 wherein the feed stream introduced intosaid reaction zone is in the gas oil boiling range.

JOSEPH C. ROEDIGER.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date Zavertnik Sept. 4, 1934 Wittenberg Oct. 16, 1934 Thiele Oct.14, 1941 Shepardson June 3, 1947 Peery May 17, 1949

1. PROCESS FOR PREPARING BITUMINOUS MATERIAL, SUITABLE AS A SATURANT FORFIBER BOARD AND OTHER PURPOSES, WHICH COMPRISES SUBJECTING THE CYCLE OILFORM A CATALYTIC CRACKING OPERATION TO THERMAL